The europium-substituted heteropolytungstate K13Eu(SiW11O39)(2) was successfully assembled into two lipids by LB technique for the first time. X-ray diffraction has shown a well defined lamellar for the LB films. The LB films have been characterized by fluorescence spectra and the characteristic luminescence behaviors were discussed. The ligand-metal charge transfer band could be observed in the spectra of the LB films, which could not be found in that of heteropolytungstate solid. The results of fluorescence spectra indicate the energy could be effectively transferred from ligands to the Eu3+ ions in the LB films and the luminescence efficiency was increased greatly. The influences of various lipids on the luminescence of polyoxometalates were investigated. The various interactions between monolayer and polyanions have different effect on the luminescence properties of europium-substituted heteropolytungstate.